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Synthesis of Single-Crystalline Core-Shell Metal-Organic Frameworks
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Coordination-Bond-Driven Dissolution-Recrystallization Structural Transformation with the Expansion of Cuprous Halide
Zi-You Zhang1, Yan Su1, Lin-Xi Shi2
1Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, College of Chemistry and Materials Science, Nanjing Normal University, Nanjing, Jiangsu 210046, China.
Inorganic Chemistry
|September 1, 2020
Summary
This study demonstrates a novel dissolution-recrystallization structural transformation (DRST) in metal-organic frameworks (MOFs), converting 2D NJNU-100 to 3D NJNU-101. This process expands copper-iodide aggregates, offering new possibilities for semiconductor and OLED materials.
Area of Science:
- Materials Science
- Crystallography
- Supramolecular Chemistry
Background:
- Metal-organic frameworks (MOFs) featuring cuprous-halide aggregates show promise for organic light-emitting diode (OLED) and semiconductor applications.
- Engineering MOF flexibility through the expansion of cuprous aggregates presents a significant challenge in materials design.
Purpose of the Study:
- To achieve a controlled structural transformation in MOFs to engineer the expansion of cuprous aggregates.
- To investigate the mechanism of dissolution-recrystallization structural transformation (DRST) and its driving forces.
- To explore the potential of the resulting MOFs as semiconductor and OLED materials.
Main Methods:
- Dissolution-recrystallization structural transformation (DRST) from 2D NJNU-100 to 3D NJNU-101.
- Observation of structural transformation using optical microscopy and powder X-ray diffraction (XRD).
- Computational simulation of aggregate expansion, ligand rotation, and metal ion reduction.
- Capture and analysis of an intermediate product (NJNU-102) to elucidate the reaction mechanism.
Main Results:
- Successfully realized DRST with significant growth of CuI-I aggregates, transforming 2D NJNU-100 into 3D NJNU-101.
- Identified unsaturated coordination nodes in NJNU-100 as the driving force for DRST via coordination bond formation.
- Captured intermediate NJNU-102, confirming DRST involves coordination bond breakage/recombination and electron transfer.
- Demonstrated potential applications of NJNU-100 and NJNU-101 as semiconductor and OLED materials.
Conclusions:
- DRST is an effective strategy for engineering MOF flexibility and controlling the growth of CuI-X aggregates.
- The transformation from NJNU-100 to NJNU-101 is irreversible and driven by specific coordination interactions.
- This work provides valuable insights into crystal engineering and the rational design of MOFs for advanced electronic applications.
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